Process for breaking petroleum emulsions



Patented Feb. 20, 1951 PRGCESSES FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Kaiser, Webster Groves, Ma, assignors to Petrolite Corporation, Ltd., VVillnington, Del., a corporation of Delaware No Drawing. Application December 13, 1948, Serial No. 65,084

11 Claims. (Cl. 252-341) This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. This invention is a continuation-in-part of our co-pending application Serial No. 726,207, filed February 3, 1947 (now abandoned). See also our co-pending applications Serial No. 8,731, filed February 16, 1948 (now abandoned, and Serial No. 82.704, filed March 21, 1949, now Patent No. 2,499,370, dated March 7, 1950). Attention is directed also to our three co-pending ap lications Serial No. 65,082, filed December 13, 1948; Serial No. 65,083, filed December 13, 1948; and Serial No. 64,456, filed December 10, 194-3 (now abandoned).

Complementary to the above aspect of the invention is our companion invention concerned with the new chemical products or com ounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, products, and the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsiiication. See our co-pending ap lication Serial No. 65,085, filed December 13, 1948.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil of commingling the demulsifier with the aqueous 2 component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

Briefly stated, the present process is concerned with the breaking or resolving of petroleum emulsions by means of quaternary ammonium compounds obtained from certain esters which are, in turn, derivatives of specific synthetic products. These products are, in turn, the oxyalkylated derivatives of certain resins herein after specified.

Thus, the present process is concerned with breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to a specific hydrophile quaternary ammonium compound, as hereinafter described. Said hydrophile quaternary ammonium compound is obtained by reaction between a basic acylated aminoalcohol in which there is at least one occurrence of the radical in which RC0 is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R is an alkylene radical having at least 2 and not more than 10 carbon atoms; and n is a small whole number varying from 1 to 10; and the molecular weight of said compound in monomeric form being at least 213 and not over 4,000; and the ester of an alphahalogen monocarboxylic acid having not over 6 carbon atoms and hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 ;carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble, phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive towards said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formulalRaOM, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radi-c cals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introtageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reduced for each phenolic nucleus; and with the,

final proviso that the hydrophile properties of the ultimate quaternary ammonium compound as Well as the oxyalkylated resin in an equal weight of xyleneare sufficient to produce-an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

For convenience, what is said hereinafter may be divided into five parts. Part ,1 will be .concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversion of the immediately aforementioned derivative into a total or partial ester by reaction with chloroacetic acid, or the like;- Part 4 will be concerned with the reaction between such esters containing a labile halogen and thetertiary amine derivatives containing a monocarboxy detergent-forming acid radical as previously specified;. and Part 5 will be concerned with the use of such quaternary ammonium compounds as demulsifiers, as hereinafter described.

PART 1" In such idealized representation n is a numeral varying from lto 13 or even more, provided that the resin is fusible and organic solvent-soluble. R is a hydrocarbon radical having at least 4 and not over 8 carbon atoms. In the instant application R may have as many as l2 carbon atoms, as in the case of a resin obtained from a dodecylphenol. In the instant invention it may be first suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and finally the phenols, for the reason that the latter require more elaborate description. i a

The alkylene oxides which may be used are actions which are not desirable, thug introducing difficulties into the resinification 'step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the highe aldehydes enter into self-resinification when treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from para-' tertiary amylphenol and formaldehyde on one hand, and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure. The production of resins from furfural for use in preparing reactants for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermediates in this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difficult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: Para-tertiarybutylphenol; para-secondarybutylphenol; para-tertiary-amylphenol; parasecondary-amylphenol; para-tertiary-hexylphenol; para-isooctylphenol; ortho-phenylphenol; para-phenylphenol; ortho-benzylphenol; parabenzylphenol; and para-cyclohexylphenol, and the corresponding ortho-para substituted metacresols and 3,5-xylenols. Similarly, one may use paraor ortho-nonylphenol or a mixture, paraor ortho-decylphenol or a mixture, menthylphe- 1101, or paraor ortho-dodecylphenol.

For convenience, the phenol has previously been referred to as monocyclic in order to differentiate from fused nucleus polycyclic phenols, such as substituted naphthols. Specifically, monocyclic is limited to the nucleus in which the hydroxyl radical is attached. Broadly speaking, where a substituent is cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic although the phenolic hydroxyl is not attached to a fused polycyclic nucleus. Stated another Way, phenols in which the hydroxyl group is directly attached to a condensed or fused polycyclic structure, are excluded. This matter, however, is clarified b the following consideration. The phenols herein contemplated for reaction may be indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and 5 positions may be methyl substituted.

The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, With the proviso that R is a hydrocarbon substituent located in the 2, 4, 6 position, again with the provision as to 3 or 3,5 methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with hydroxyl position as one:

The manufacture of thermoplastic phenolaldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted by a hydrocarbon group, and particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided it is present in the 3 or 5 position.

Thermoplastic or fusible phenol aldehyde resins are usuall manufactured for the varnish trade and oil solubility is of prime importants. For this reason, the common reactants employed are butylated phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difficulty, while when a water-insoluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantit of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and Wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufficient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when high aldehydes are used an excess of aldehydic reactant can be distilled off and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that con siderably increased amounts of formaldehyde may be used, asmuch as two moles of formaldehyde, for example, per mole of phenol, or even more, with the result that only a small part of such aldehyde remains uncombined or is subsequently liberated during resinification. Structures which have been advanced to explain such increased use of aldehydes are the following:

Such structures may lead to the production of cyclic polymers instead of linear polymers. For reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does no v exclude resins of such cyclic structures.

Sometimes conventional resinification precedure is employed using either acid or alkaline catalysts to produce low-stage resins. vSuch resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular Weight, by heating along with the employment oi vacuumv so as to split off water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehyde used may and does usually affect the length of the resin chain. Increasing the amount of the aldehyde, such as form aldehyde, usually increases the size or molecular weight of the polymer.

In the hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield prcducts usually having definitely in excess of '3 nuclei. In other words, a resin having an averof l, or 5 nuclei per unit is apt to be formed as a minimum in resinification, except under tain special conditions where dimerization in y occur. 4

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils or refluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinct- 1y over'the'above values, for example, it may-average '7 to 15 units. low-stage resin or low-stage intermediate is employed to mean a stage having 6 or '7 units or even less. In the appended claims we have used low-stage to mean 3 to '7 units based on average molecular weight.

The molecular weight determinations, of course, require that the product be completely soluble in the particular solvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently perhaps, the boiling point in an ehullioscopic 'method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2369 and 2314: (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylainine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947) Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no 7 catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfa-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in detail. However, We have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those ref rred to as highstage resins, are conveniently obtained by subjecting lower molecular weight resins to vaccum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vaccum.

We have found that under the usual conditions of resinification employing phenols of the kind here described, there is little or no tendency to form binuclear compounds, 1. e., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly where the substituent has 4 or 5 carbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specified herein, there may be some tendency to dimerization. The usual procedure to obtain a dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted Sometimes the expression 9 phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employed may be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market, we have found it particularly desirable to use the procedures described elsewhere herein, and employing a combination of an organic sulfo-acid and a mineral acid as a catalyst, and xylene as a solvent. By way of illustration, certain subsequent examples are included, but it is to be understood the herein described invention is not concerned with the resins per se or with any particular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof. They phenol-aldehyde resins may be prepared in any suitable manner.

oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous phase. It can, for example, be carried out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension. Since the melting points of the resins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or suspension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having a solvent present during the resinifying stage if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards Water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin (decahydronaphthalene) tetralin (tetrahydronaphthalene), ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more. Solvents such as dichloroethylether, or dichloropropyletner may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations.

The use of such solvents is a convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37 92; to 40% formaldehyde, is the preferred reactant When such solvent is used it is advantageously added at the beginning of the resinification procedure or before the reaction has proceeded very far.

The solvent can be removed afterwards by distillation with or without the use of vacuum, and

a final higher temperature can be employed to complete reaction if desired. In many instances it is most desirable to permit part of the solvent, particularly when it is inexpensive, e. g., xylene, to remain behind in a predetermined amount so as to have a resin which can be handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ reactants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzene. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in the neighborhood of of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol, which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be sufficient to cause insolubility at the completion of the resinification stage or the lack of hydrophile properties at the completion of the oxyalkylation stage.

The exclusion of such trifunctional phenols as hydroxybenzene or metacresol is not based on the fact that the mere random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxy-methylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to non-hydrophilic products resulting from the oxyalkylation procedure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is produced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particu larly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause cross-linking in a conventional resinification procedure, or in the oxyalkylation procedure, or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing intermediates to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described in Example 1a of our Patent 2,499,370, granted -March 7., 1950. If the resin so obtained is .sol-

vent-soluble in any one of the aromatic ;or other solvents previously .referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is employed of approximately 150 to 165 C. with addition'of at least 2 andadvantageousl up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation is advantageously conducted so as to require from a few minutes up to 5 to 10 hours. If the product so obtained is solvent-soluble and self-dispersing or emulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the standpoint of trifunctional phenol content. The solvent may be removed prior to the dispersibil-ity or emulsifiability test. When-a product becomes rubbery during oxyalkylation due to the presence of a small amount of trireactive phenol, as preiously mentioned, or for some other reason, it may become extremely insoluble and .nolonger qualifies as being hydrophile as herein specified.

Increasing the size of the aldehydic nucleus, for instance using heptaldehyde instead .of formaldehyde, increases tolerance for trifunctional phenol.

The presence -'of -.a trifunctional aor tetrafunctionalphenol (such as resorcinol or bisphenol A) is apt to produce {detectable (cross-linking and insolubilization but will not necessarily do so,

especially if the proportion is small. Resinification involving difunctional phenols only may also produce insolubilization, although this seems to be an anomaly or a contradiction of what is sometimes said in regard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. 'This appears to be contradictory to what one might expect in light of the theory of functionality in resinification. 'It is true that under ordinary circumstances, or rather under the circumstances of conventional resin manufacture, the procedures employing difunctional phenols are very apt to, and almost invariably do, yield solvent soluble, fusible resins. However, when conventional procedures are employed in connection with resins for varnish manufacture or the like, there 'is involved the matter of color, solubility in oil, etc. When resins of the same type are manufactured for the herein contemplated purpose, i. e., as a raw material to be subjected to oxya'lkylation, such criteria of selection are no bibliography of such investigations, see Car-swell,

'Phenoplasts, chapter 2. These investigators limited much .of their work to reactions involving phenols .having two or less reactive hydrogen atoms. Much of what appears in these :most recent and most up-to-date investigations :is pertinent to the present invention insofar that much of it is .referringito resinification involving difunctional phenols.

For the moment, it may be simpler to consider a most typical type-.of fusible resin and forget for the time that such resin, at least under certain circumstances, is susceptible to further compli- :cations. Subsequently in the text it will be pointed out thatcross-linking or reaction with excess formaldehyde may take placeeven with one of .such most typical :type resins. This point is :made for the :reason that insolubles must be avoided in order "to :obtain the products herein :contemplated for "use :as reactants.

The typical type of fusible resin obtained from a para-blocked :or ortho-blocked phenol is clearly differentiated from the Novolak type or resole type of resin. Unlike the :resole type, such typical type para-blocked or ortho-blocked phenol resin may be heated indefinitely without passing into anin-fusible stage, and in this respect is similar to .a Novolak. Unlike the Novolak type the addition of a further reactant, for instance, more aldehyde, does .not ordinarily alter fusibility of the difunctional phenol-aldehyde type resin but such addition to a-Novolak causes cross-linking by virtue of the available third functional position.

What has been said immediately preceding is subject to modification in this respect: .It is well known, for example, that difunctional phenols, for instance, :paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-harden'able resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an longer pertinent. Stated another way, one may use more drastic conditions of resinification than those ordinarily employed to produce resins for the present purposes. 'Such more drastic condi tions of resinification may include increased amounts of catalyst, higher temperatures, longer time of reaction, subsequent reaction "involving heat alone or in combination with vacuum, etc. Therefore, one is not only concerned with the resini-fication reactions which yield the bulk of ordinary resins from difunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which-are of importance in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times,and they may lead to cross-linking. V

In this connection it may be' well to point out that part of these reactions are now understood or explainable to a greater or lesser degree in light of a most recent investigation. Reference is made to the researches of Zinke and his co workers, Hultzsch and his associates, and to Von Eulen and his co-workers, and others. .As to a alkaline :c'atalyst. This peculiar hardening or curing \or cross-linking of resins obtained from difunctional phenols has been recognized by various authorities.

The intermediates here-in used must be hydrophile or sub-surface-active or urface-active as hereinafter described, and this precludes the formation of insolubles during resin manufactrue or the subsequent stage of resin manufacture where heat alone, or heat and vacuum, are employed, or in the oxyalkylation procedure. In its "simplest presentation the rationale of resinific'a'tion involving formaldehyde, for example, and a di-functiona'l phenol would not be expected to form cross-links. However, cross-linking sometimes occurs and it may reach the-objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difiiculty in preparing a very large number of resins of various types and from various reactants, and by means of different catalysts by different procedures, all-of which are eminently suitable for the herein deseribedpurpose.

Now returning to the thought that cross-linking can take place, even when difuncti'onazl phenols are used exclusively, attention is directed to the following: Somewhere during the course of resin manufacture there may be a potential cross-linking combination formed but actual cross-linking may not take :place :until the subsequent stage is reached, i. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in terms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CHzOH radical and H atom may not lie in the same plane in the manufacture of ordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly formaldehyde, insofar that a slight variation may, under circumstances not understandable, produce, insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in t -e proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of these resins.

All that has been said previously herein as regards resinification has avoided the specific reference to activity of a methylene hydrogen atom. Actually there i a possibility that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge, or some other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resin derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its themoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the preesnt invention is concerned, it is obvious that a resin to be suitable need only be sufiiciently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization of gel formation, or rubberiness, as previously described. Thus resins which are, strictly speaking, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, 01' have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

The polyhydric reactants, i. e., the oxyalkylation-susceptible, Water-insoluble, Organic 50]- vent-soluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as intermediates to produce the products used in accordance With the invention, are exemplified by Examples Nos. la through 103a of our Patent 2,499,370, granted March 1950, and reference is made to that patent for examples of the oxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of para-butylphenol and para-amylphenol, or a mixture of para-butylphenol and para-hexylphenol, or parabutylphenol and para-phenylphenol It is ex tremely difficult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producing simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the three classes, is contemplated and here included for the reason that they are obvious variants.

Having obtained-a suitable resirr of the kind described, such resin is subjected to" treatment with a w molal reactivealpha beta'oleiin oxide so as torende'r the ro uct distinctly hydrophile in nature as indicated by the fact'that'it'becomefs slf-inulsifiablei or miscible or soluble in water, or self-dispersible, or has emulsifying: properties; The olefin oxides employed are characterized by the fact'that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene' oxide, glycide; and methylglycide. Glycide may be, of course, considered as hydroxy propyleneoxide andm'ethyl glycid'e as a hydroxy butylene oxide; In any event, however; all such reactants contain the reactive ethylene oxide ring and may be best considered. as derivatives of or substituted ethyl ene oxides. The solubilizing eiiect of the'oxideis directly proportional to the" percentage of oxygen present; or specifically, to the oxygen' 'carbo'n ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2; In glycide, it is- 2:3, and in methylglycid'e;

1:21 In such compounds, the'ratio is very favorable to the production of hydrophile or surface active properties. However, the ratio, in propyle'ne'oxide, is 1:3, and in'butylene oxide, 1:4. Obviously, suchlatter two reactants are satisfactorily' employed only where'theresin composition is' such as to make incorporation of the desired property practical. In'oth'e'r cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkyl ene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules hav been attached to the resin molecule,- oxyalkylation may be satisfactorily continued using the more favorable members of the class,- to produce the desired hydrophile product. Used alone; these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios. l'hus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is' more effective than butylene' oxide. Hydroxy propylene oxide (glycide) is more eiiective than propylene oxide. Similarly, hydroxy butylene oxide (methyl: glycide) is' more eilective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less" reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care;

The oxyalkylation of resins of the kind from which the initial reactants used in the practice of thepresent invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch) In a general way, the method employed is substantially the same procedure as used for oxy 1'6' alienati n; of: other organic materials nav ihs 're a'ctiv henolic groups r ltmay 'sulf'onic aci d,'it mayfbenece'ssary and is usually advantageous to add aln' amount of alkali equal stoic'hiometrically' to such acidity, and include added'alkali ever and above this amount as the alkalinecatalyst;

in presence of an' inert solvent such as xylene,

cymene, decalin, ethylene glycol diethylether, di. ethylene'glyc'ol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and" may be permitted toflbepresent in the final product used as a demulsifier, itis our temperatures, if required.

Howeveneven in the instance of high-"melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction ofapproximately 2 or 3 moles of ethylene oxide, for exampleper phenolic nucleus, there is a definite drop in the hardness and'melting point of the resin. At this stage; if xylene or a similar solvent has been added, it can be eliminated by distillation vacuum distillation is desired) and the subsequentintermediate, being comparatively soft and solvent-freapau be reacted further in the usual manner with ethylene oxide or some other suitable reactant.

Another proeedureis to continue the reaction to completion with such solvent present and then enmmatethe solvent by distillation in the custernary manner.

Anoth U oxide or butylene oxidepas a solvent as; well as areactant isms earlier stages along with ethylene oxide, forin'stance, by dissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the v original resin dissolved in propylene oxide o'r'biitylen'oxide, or a mixture which in cludes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hyproperties are obtained. Since ethylene 'r h e oxide is more reactive than propylene oxide or butylene' oxide, the final product may containsonie unreacted propylene'oxide or butylene oxide which can be eliminated by volatilization or distillation in my suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic soivent, Fusibl resins invariably are soluble in one or more organic'solve'nts such as those mentionedelsewhere herein. It is to be emphasized, hbwev'er, that the organic Solvent er suitable procedure is to use propylene employed to indicate or 'assure'tliat the resin meets this requirementneed not be the one used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However, where a resin is soluble in an organic solvent, there are usually available-other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 200 mesh, and a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is solublein an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive hydroxyl groups and are oxyalkylation susceptible Considerable of what if; said immediately hereinafter is concerned with ability to vary the hydrophile properties of the hydroxylated intermediate reactants from minimum hydrophile properties to maximum hydrophile properties. Such properties in'turn, of course, are effected subsequently by the acid employed for esterification and the quantitative nature of the esteriflcation itself, i. e., whether it is total or partial, and also by the basic acylated amino-alcohol used to obtain the final product for use in the process of the present invention. It may be well, however, to point out what has been said-elsewhere in regard to the hydroxylated intermediate reactants. See, for example, our co-pending applications, Serial Nos. 8730 and 3731, both filed February 16, 1948, and Serial No. {12,133,1iled August 2, 1948 (all three cases now'abandoned), and Serial No. 42,134, filed August 2, 1948. The reason is that the reactions, depending on the acid and the basic acylated amino-alcohol selected, may vary the hydrophile-hydrophobe balance in one direction or the other, and also invariably causes the development of some property which makes it inherently different from the reactants from which the derivative is'obtained.

Referring to the hydrophile'"hydroxylated intermediates, even more remarkable 'and equally difficult to explain,-are the versatility and the utility of these compoundsconsidered as chemical reactants as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately inexcess thereof areintroduced per phenolic hydroxyl. Such minimum 'hydrophile property or sub-surface-activity or minimum surface-activity means that the product shows at least emulsifying properties-or self dispersion in cold oreven in warm distilled water (15 to 40 C.) in' concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately. high temperatures aid in reducing the viscosity of the; solute. under examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solu tion takes place to give a homogeneous phase as the mixture cools. Such sel f.dispersion tests are conducted in the absence of a insoluble solvent. r

When the hydrophile hydrophobe balance is above tlieindi'cated minimum (2' moles of ethylene oxide per phenolic nucleusor theequiva'lent) weight of xylene and mix such solution with one,

two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not sufficient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance to and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable), such sol or dispersion is referred to as at least semi-stable in the sense that sols, emulsions or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 0.). Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture, i. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of con- Ventional measurements hereinafter described. One outstanding characteristic property indicating surface'activity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the hydrophile properties of the final product. The principal involved in the manufacture of the herein contemplated compounds for use as poly-- hydric reactants, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are self-- emusifying; that is, when shaken with water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent. such as xylene, an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most efiicacious results are obtained with products which do, not have hydrophile properties beyond the stage ofself-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be. measured by determining the surface tension and the interfacial tension against paraffin oil or the like. At the initial and lower stages of oxyalkylation, surface'acivity is not suitably determined in this same manner but one may employ' an emulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal Weight of xylene. such 50-50 solution is then mixed with 1-3 volumes of water and If in doubt as to this property, comparison with. a resin obtained from para-tertiary butylphenol.

and formaldehyde (ratio 1 part phenol. to 1.1

formaldehyde) using an acid catalyst andthen followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, ishelpful;

Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, isv

considered the equivalent of xylene for the. purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surface-active characteristics in the polyhydric reactants used in accordance with this invention. They dissolve or disperse in water; and such'dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-'surface-activity) tests for emulsifying properties or self-dispersibility are useful.

The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide,

have been introduced for each phenolic nucleus.

In doubtful cases, comparison canis themolecular size. of; the resin chain resulting Th e en e. yl ne or a u val n wa n u le sq eet may ma k he i t at which a solvent-tree product on mere dilution in a test ube xhi its se i-em l fi t on- F r this reason, it? it. is desirable to determine-the p r ma m t wh re se mul ific in than it i be ter t lim na e the xyl n or equivalent from a small portion of the reaction mixture and test; such portion. In some cases, such xylene-free resultant may show initial or inp n h ph le p op r ies. wh r s: n p ence of xylene such; propertieswould not benoted. In other cases, the first objective indication of hydrophile properties maybe the-capacity of the material. to emulsify' an insoluble solvent such as xylene. It isto be emphasized. that. hydrophile properties herein referred to; are such. as those exihibited by incipient sel f -emulsificatior or; the presence of: inu lsifying properties andgo through the range, ofhomogeneous dispersibility or admixture with water even in presence of added water-insolublesolvent and minor proportions of common electrolytesas occur in oilfield brines.

Elsewhere, it; is, pointed out that an emulsifica tion test may be-usedto deter-mine ranges ofsurface-activity and that such emulsification tests employ a; xylene; solution; Stated another. way, it isv really immaterialwhether a xylene solution produces a solor whethenitmerely produces an emulsion.

In light, of whathas been said previously in regard to the variation of range of hydrophile properties, and} also in lightof what has been said, as to the variation in the. efiectiveness of various alkylena oxides, and mostparticularly of all ethyleneoxide to introduce hydrophile; char acterg. it becomes obyious that there is a wide variation: in the amount-of. alkylene oxide emp1oyed, as long; asitis atleast 2-molesper phe nolic nucleus, for producing; products: useful for the practiceof this invention. Another variationfrom reaction between the. difunctional phenol and the, aldehydesuch, as formaldehyde.

of the.- zgesin. polymer obtained varies somewhat with the conditionsof; reaction, the proportions.

of; reactants, the; nature of, the.- catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as-her-ein described,

" particularly in theab sence of; a secondary heatdrastic conditions of i esini'fication one usuallyfinds that higher molecular weights areindi-= cated-, by higher,- melting points of the resins and a tendency to'decreasedisolubility. See-what has been said" elsewhere herein in regard to a secondary step inyolving the heating'of a resin 0-? 7 'm: preparing the resin. A, combination, of.

wither withouttheuse off.vacuum. 7

We have. previously.pointediloutthat either an, alkaline or. acid; catalyst. is; advantageously used catalysts is sometimes used in two stages; for. instance, an alkaline, catalyst .is sometimes employed in a first; stage, followed. by;v neutralization dr difio .1 mall amountio z, id alyst- It iswell known thatthe and-;n a;tur;e or structure 21 r in a second stage. It is generall believed that evenin the presence of an alkaline catalyst, the number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. It is possible that such groups may appear in the finished resins prepared solely with an alkaline catalyst; but we have never been able to confirm th s fact in an examination of a large number of resins prepared by ourselves? Our preference, however, is to use an acid-catalyzed resin, particularly employing a formaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. probable that in acid-catalyzed resinifications, the methylol structure may appear only momentarily at the very beginning of the reaction and in all probability is converted at once into a more complex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to prepare polyhydric reactants for use in the preparation of compounds employed in the present invention, is to determine the hydroxyl value by the Verley-Bolsing method or its equivalent. The resin as such, or in the form of a solution as described, is then treated with ethylene oxide in presence of 0.5% to 2% of sodium methylate as a catalyst in step-wise fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance a few minutes to 2 to 6 hours, but in some instances requires as much as 8 to 24 hours. is from 125 to 225 C. The completion of the reaction of each addition of ethylene oxide in step-wise fashion is usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as five or six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the stepwise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved and it is often advantageous to As a matter of fact, it is,

A useful temperature range add the alkylene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pltch-like resin at ordinary temperatures. Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation and particularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated res ins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or subsurface-active range without examining them by reaction with a number of the typical acids and the basic acylated amino-alcohols herein described and subsequently examining the resultant for utility, either in demulsification or in some other art or industry as referred to elsewhere, oras a reactant for the manufacture of more com-- plicated derivatives. A few simple laborator tests which can be conducted in a routine man ner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to 1; 6 to 1; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to l or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go to the trouble of 23 calculating molecular weights, one can simply arbitrarily prepare compounds containingethyb ene oxide equivalent to about 50% to" 75% by weight, for example 65% by weight,- of the" resin to be oxyethylated; a second example using approximately20'0% to 3Q by weight, and-a-thirdexample using about 500 to 750% by weight, to explore the range of hydrophile hydrophobe balance.

A' practical examination of the factor of oxyalkylation level can be made by a very simple test using a'pilot plant autoclave having a capacity of about 10 to 15 gallons as hereinafter diescribed.- Suchlaboratory-prepared routine compounds can then be tested for solubility and, generally speaking; this' is all that is-requ-ired to give a" suitable variety covering the hydrophile-hydrophobe range. 'All these tests; as stated, are intended to be routine tests andnoth-' ing more. They are intended toteacha person, even though unskilled in oxyethy'lationor oxyalkylation, how topreparein a perfec'tly' arm trar y manner, a series of compounds 'illus'tr'atihg the hydrophile-hy'drbphobe range.

If' one purchases a thermoplastic or fusible resin in the open market selectedfrom a suitable number which are available, one might have to make certain determinations-in order to make the quickest approach to the appropriateoxy alkylation range. For instance, one should-knew ('a) the molecular size, indicating the number" of phenolic units; (17) the nature ofthe aldehydic: residue; which is usually CH2: and (03 the-natureof the substituent, which is usually butyl amy'l,

ternal structural units of-the'resinof the follcw ing over-simplified formula:

("112:1 to 13. or even more is given approximately by the formula: (mol. weight of phenol -2) plus moLweight of methylene or substituted methylene radical. The molecularweight of the resin would be n times the value for the internal limit plusthe values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring. internal unit except that it has one extra hydrogen. Theright-hand terminal unit lacks the methylene bridge element. Using one internal'unit: of a resin as the basic element, a resins molecular. weight is given approximately by taking ('ni plus 2) times the weight of the internal element;

Where the resin molecule has onrycphenolic nuclei as in the structure shown, this calculation Using such anapproximate weight, one need only introduce; for example; twomolal" weights ofethylene oxide or slightly more; per phenolic nucleus, to produce'aproduct-of minimal hydro-- phile character. Further oxyalkylation-gives enhanced hydrophilecharacter;- Although wehaii 24 l prepared andtested a large number of. oxyethyl ated products of th e type described herein, we have found no instance where the use of less than 2 moles of ethyleneoxide per phenolic nucleus gave desirable products 7 I Exampleslb through 18b, and the tables which appear in columns 51 through 56 0t our said Patent 2,499,370 illustrate oxyalkylation prpa: note from resins which are useful; as inter mediates for producing the quaternary arnrrio mumcompounds used in accordance with the present application, such examples giving exact and complete details for carrying" out the airyalkylation procedure. V

The resins, prior to oxyalkylation, vary; from tacky,- viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, to a'i deep" red or even almost black. In the manufacture of resins, particu larly' hard resins, as the reaction progresses the reaction mass frequently goes through a'liquid state to a sub-resinous or semi-resinous state,

often characterized by being tacky or sticky, to

a final complete resin.- As the resin is subjected "to oxyalkylation these: same physical changes tend to take place'in reverse; If one starts withi a solid resin, oxyalkylation tends to make it tacky or semi-resinous and further oxyalkylatio'n' makes the tackiness disappear and changes the product toa liquid. Thus, as the resinis oxyalkylated it decreases in viscosity, that is, be comes more liquid or' changes from'a solid ma liquid, particularly when it is converted to the" Water-dispersible of water-soluble stage. The

. color of the oxya-lkylated derivative is usually considerably lighter than the original product from which it is made, varying from a pale strawcolor to an amber or reddish amber. The vis= cosityusually varies from that of an oil, like castor oatmeal-,0: a thick viscouss'irlm. Some" products are waxy. The presence of a solvent, such as 15 xylene or=the like, thins the viscosity considerably and also reduces the color in dilu tibn. No undue 'sighificance need" be attachedto the color for the reason that if the same, com-- pound is prepared in" glass and in iron, the latter usually has somewhat darker color. Iftheresins are prepared ascustomarily employed in varnish resin. manufacture, i. e'., a procedure that ex-- cludes-thepresence of oxygenduring the resinifi,

cation and subsequent cooling" of the resin, then" of coursethe'initialresinis much lighter color.

We have employed some" resins which mac-1y are almost water-white and also yi'el'dalighter colored final product.

Actually; in considering the ratio or airmen oxide to add, and we have previously pointed out that this can be pre-determined using laboratory' tests, it is our actual preferen'ce from a practical standpoint to make tests on a; small pilot plant scale.- Our reason-{for so doing s that we-m'ake one mn, andonly one, and that" we: have a" complete series which shows the progressive effect of introducing the oxya-lkyl'at ing agent;-for 'instance} tne et y1emoxymamas.

Our preferred'procedure 'isas follows: We-prepare a suitable resin;- or" fcntha-t-niatter, pur chase it theopen market. pounds ofresin and l pounds of xylene and place the resin and xylenein a suitable autoclave with an open-reflux condenser. We prefer toheaty and stiruntil thesoluti'oh is-complete: We have pointed out that soft" resins which "arefiuid or semi-,fluid -can be? readily prepared in v'ario'us We employ 8 j phenol, ortho hydroxydiphenyl, ortho-decylphenol, or by the use of higher molecular weight aldehydes than formaldehyde. If such resins are used, a solvent need not be added but may be added as a matter of convenience or for comparison, if desired. We then add a catalyst, for instance, 2% of caustic soda, in the form of a 20% to 30% solution, and remove the water of solution or formation. We then shut oif the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We prefer a temperature of about 150 C. to 175 C. We also take samples at intermediate points as indicated in the following table:

Pounds of Ethylene Percentages Oxide Added per 8-pound Batch Oxyethylation to 750% can usually be completed within 30 hours and frequently more quickly.

The samples taken are rather small, for instance, 2 to 4 ounces, so that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, i. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be sufiicient to indicate hydrophile character or surface activity, i. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorption at the interface, for example, a gasliquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the usual ways using a DuNouy tensiometer or dropping pipette, or any other procedure for measuring interfacial tension. Such tests are conventional and require no further description. Any compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to a greater extent, 1. e., those having a greater proportion of alkylene oxide, are useful as polyhydric reactants for the practice of this invention. Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in solvent, will yield an insoluble rubbery product, i. e., a product which is neither hydrophile nor surface-active, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one may have a solvent-soluble resin derived from a mixture of phenols having present 1% or 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of 2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active reactant which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable reactant. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubilit and also the fact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness, or even the tendency toward a rubbery stage, is not objectionable so long as the final product is still hydrophile and at least subsurface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which we want to make here, however, is this: Stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked resin molecule and if such molecule is oxyalkylated so as to introduce a plurality of hydroxyl groups in each molecule, then and in that event if subsequent etherification takes place, one is going to obtain cross-linking in the same general way that one would obtain cross-linking in other resinifi cation reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide. This may be done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or 5 times as long to introduce an equal amount of ethylene oxide employing the same temperature, then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it ma be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins'herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble sol- 27. l 28 vent such as to of xylene. Further ployed should be non-reactive to the alkylene oxyalkylation, particularly oxyet'hylation, may oxide employed. This limitation does not apply then yield a product which, instead of giving a to solvents used in cryoscopic determinations for clear solution as previously, gives a very milky obvious reasons. Attention is directed to the solution suggesting that some marked change has 5 fact that various organic solvents may be emtaken place. One explanation of the above ployed to verify that .the ,resin is organic solchange is that the structural unit indicated in vent-soluble. Such solubility test merely characthe following way where 811 is a fairly large terizes the resin. The particular solvent used number, for instance, 10 to 20, decomposes and in such test may not be suitable for a molecular an oxyalkylated resin representing a lowerdegree 10 weight determination and, likewise, the solvent of oxyethylation and a less soluble one, is genused in determining molecular weight may not erated and a cyclic polymer of ethylene oxide is be suitable as a solvent during oxyalkylation. produced, indicated thus: For solution of the oxyalkylated compounds, or

HH non 1 1 -,R .O(CQH40)5,,H BQO(CQHAO)MH+ C2 1 O n I \im This fact, of course, presents no difficulty for the their derivatives a great variety of solvents may reason that oxyalkylation can be conducted in be employed, such as alcohols, ether alcohols, each instance stepwise, or at a gradual rate, and cresols, phenols, ketones, esters, etc., alone or samples taken at short intervals so as to arrive with the addition of water. Some of these are at a point where optimum surface activity or hymentioned hereafter. We prefer the use of bendrophile character is obtained if desired; for zone or diphenylamine as .a solvent in making products for use as polyhydric reactants in the cryoscopic measurements. The most satisfacpractice of this invention, this is not necessary tory resins are those which are soluble in xylene and, in fact, may be undesirable, i. e., reduce the or the like, rather than those which are soluble efficiency of the product. v only in some other solvent containing elements We do not know to what extent oxyalkylation other than carbon and hydrogen, for instance, produces uniform distribution in regard to oxygen or chlorine. Such solvents are usually phenolic hydroxyls present in theresin vmolepolar, semi-polar, ,or slightly polar in nature cule. In some instances, of course, such districompared with xylene, cymene, etc. bution can not be uniform for the reason that Reference to cryoscopic measurements is conwe have not specified that the molecules of cerned with the use of benzene or other suitable ethylene oxide, for example, be added in mulcompound as a solvent. Such method will show tiples of the units present in the resin molecule. that conventional resins obtained, for example, This may be illustrated in the following manner; from para-tertiary amylphenol and formalde- Suppose the resin happens to have five phehyde in presence of an acid catalyst, will have. nolic nuclei. If a minimum of two moles of a molecular weight indicating 3, 4, 5 or someethylene oxide per phenolic nucleus are added, What greater number of structural units per t would mean an addition of 10 moles f 45 molecule. If more drastic conditions of resiniethylene oxide, but suppose that one added 1-1 ficatien are ployed or if such low-sta resin moles of ethylene oxide, or 12, or 13, or 14 moles; is subjected to a vacuum distillation treatment obviously, even assuming the most uniform disas previously d, o e obtains a resin of tribution possible, some of the 'polyethyleneoxy a distinctly h r molecular W ht- Any m radicals would contain 3 ethyleneoxy units and leculal' Weight determination u d, Whether s e w u1d, contain 2, The f r it i jmposcryoscopic measurement or otherwise, other than sible to specify uniform distribution in regard the Conventional Cryeseepic one oy g t th entrance f th ethylene oxide or other zene, should be checked so as to insure that it xyalkylafing t- For t tt if one gives consistent values on such conventional were to introduce 25 moles 0f ethylene oxide resins as a control. Frequently all that is necesthere is no way to be certain that all chains of Sery to make an pp i i n of the molecu ar ethyleneoxy units would have 5 units; there weight range is to make a comparison with the might be some having, for example, 4 and 6 dimer obtained by chemical combination of two units, or for that matter 3 or 7 units. Nor is moles of the Same phenol, and one mole of the there any basis for assuming that the number same a1dehyde under conditions to insure of molecules of the oxyalkylating agent added to dimenzation- AS to the preparation of such each f the molecules of the resin is the same, dimers from substituted phenols, see Carswell, or dififerent. Thus, where formulae are given to Phenoplastsr page The increased Viscosity illustrate or depict the oxyalkylated products, resinousFhamcter' and qecreased SPWbiIiFY, distributions of radicals indicated are to be sta- 60 f the hlgher polymers m compansm? Wlth the tistically taken. We have, however, included dlmer frequently are all that Is reqmred to specific directions and specifications in regard z gl i f gg g fgfg fg 3 or more Strucgg g i g g? of g f q or 2 23 Ordinarily, the oxyalkylation is carried out in 0 any 0 er oxya y mg agen O autoclaves provided with agitators or stirring add. devices. We have found that the speed of the In regard to solubility of the resins and t agitation markedly influences the reaction time. oxyalkylated compounds, and for that matter In some cases, the change from slowspeed agiderivatives of the latter, the following should cation, for example, in a laboratory autoclave be noted. In oxyalkylation, any solvent emagitation with a stirrer operating at a speed of 60 to 200 R. P. M., to high speed agitation, with the stirrer operating at 250 to 350 R. P. M., reduces the time required for oxyalkylation by about one-half to two-thirds. Frequently xylene-soluble products which give insoluble prod ducts by procedures employing comparatively slow speed agitation, give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or curtailment of opportunity for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturin results from continuous oxyalkylation, that is, an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation.

Previous reference has been made to the fact that in preparing compounds of the kind herein described, particularly adapted for demulsification of water-in-oil emulsions, and for that matter for other purposes, one should make a complete exploration of the wide variation in hydrophobe-hydrophile balance as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. This can be done conveniently in light of what has been said previously. From a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriate selections in which the molal ratio of resin equivalent to ethylene oxide is one to one, 1 to 5, 1 to 10, 1 to 15. and l to 20. Furthermore, in making these particular runs we have u ed continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sufiiciently great to pass into the autoclave, or else we have used an arrangement which, in essense, was the equivalent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used volumetrically. Such procedure and arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five diiferent variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously, if reaction is not started at the beginning of the reaction period. Since the addition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (b) amount of cooling Water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other Words, by experience we have found that if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylation is complete. We have also indicated the maximum pressure that we obtained or the pressure range. Like-- wise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period. ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examining the columns headed Starting mix, "Mix at end of reaction, Mix which is removed for sample, and Mix which remain as next starter.

The re ins employed are prepared in the manner described in Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were repared in 10 to l5-gallon electro-vapor heated synthetic resin pilot plant reactors, as manufacfactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their bulletin No. 2087. issued in 1947, with specific reference to specification No. 71-3965.

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, to one gallon, one can proceed through the entire molal stage of 1 to l, to 1 to 20, without remaking at any intermediate stage. This is illustrated by Example 10 1b. In other examples we found it desirable to take a larger sample, for instance, a 3- gallon sample, at an intermediate stage. As a result it was necessary in such instances to start with a new resin sample in order to prepare suflicient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were by-passed or ignored. This is illustrated in the tables where, obviously, it shows that the starting mix was not removed 75 from a previous sample.

Phenol for resin: Pam-Emor Date, june 22, 1948 Aldehyde 107 mm.- Formaldehyde [Resi'n' made in pilot plant size batch, a roximamy 25 pounds, corresponding to s. of Patent 2.495.370 but this batch designated 10411.]

Mix Which is Mix Which Re- Starting Mix figg g g of Removed for mains as Next Sample Starter Max. Max. Time v Pressure 'lempgmhrs? Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. 'Lbs. lure Res- 1,593 801- Res- 5% 801- Res- 5?? S01 Resfig vent in vent in v vent in vent in First Stage Resin to EtO Molal Ratio 1 0 14. 15. 75 4. 0 3. 3. 1. 0 10. 9 12. 1 3. 0 80 159 $4 I EX. No. 1045.... v

Secorid Stage Resin to EtO Molal Ratio 1. 12.1 3.0 10.9 12.1 15.25 3. 77 4.17 5.31 7.13 7.93 9. 94 158 ST EX. No. 1055....

Third Stage Resinto EtO I Molal Ratio 1 7. 13 7. 93 9. 94 7. 13 7. 93 19. 69 3. 29 3. 68 9. 04 3. 84 4. 25 10. 65 60 173 $6 FS Ex. N'o. 10Gb- Fourth Stage Resin to 13150.... v Molal Ratio 1 3. 84 4. 25 10. 65 3. 84 4. 25 16. 15 2. 04 2. 21 8. 55 1. 2. 04 7. 0 220 160 M) RS Ex. N0. 1071:.-. 1

Fifth Stage Resiri to EtO. Molal Ratio 1:20- 1.80 2.04 '7. 60 1. 80 2.04 10. 2 190 150 16 Q5 Ex.No.108b...

I'=Insoluble. ST Slight tendeno'y Date, Time 18, 194 8 Phenol for resin: Nortylphnol Aldehyde for resin: Formaldehyde toward becoming soluble. FS'=Fairly soluble. RS=Readily soluble. QS=Quite soluble.

[Resinmad'e in pilot plant size batch, approximately 25 pounds, corresponding t0'70i1 of iatent 2,499,370 but this batch designated 109m] 7 7 Mix Which is Mix WVhich Re- Starting .Mix figg figg of Removed for mains as Next ample Starter Max. Max. Time e bull. Tenzpglfiahrs Solubility l b s. gbs. Lbs Ifibs. Lbs LRbs. Lbs abs. Lbs

c eso eso eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage ResintoEtO. Molal Ratio 1:1. 15. 0 15. 0 0 15. 0 15. 0 3 5. 0 5. 0 1. 0 19. O 10. 0 2. 9 50 150 1% ST EX. N0. 1091).

Second Stage Resin to EtO H Molal Ratio 1:5. 10 10 2. 0 10 10 9. 4 2. 72 2. 72 2. 56 7. 27 7. 27 6. 86 147 2 DT Ex.No.110b

Third Stage Resin to EtO.., 1 Molel Ratio 1:10; 7.27 7. 27 6. 86 7. 27 7. 27 13. 7 4. 16 4. 16 7. 68 3. 15 3. 15 5. 95 1% S Ex. No. 111b Fourth Stall/e Resint0Et0 Mol'al Ratio 1:15. 3. 15 3.15 5. 95 3. 15 3.15 8. 95 1. 05 1. 05 2. 95 2.19 2.10 6. 09 220 174 2% S EX. N0. 1120"--- Fifth Stage Resin to EtO... Molal Ratio 1:29 2. 1O 2. 10 6. 90 2. 10 2. 10 8. 00 220 183 93 VS Ex. No. 1135...

S=Solub1e. ST=S1ight tendency toward solubility. DT=Definite tendency toward solubility. VS=Very soluble.

Mix Which is Mix Which Re- Starting Mix g g fig of Removed for mains as Next Sample Starter Max. Max. Time Pressure Temp erahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Sol- Res- Sol- Res- Sol- Res- Sol- Resvent in vent in vent in vent First Stage Resin to Et0 Molal Ratio 121.. 13. 65 16.35 0 13.65 16.35 3.0 9. 11. 45 2. 1 4.1 4.9 0.9 150 1% NS Ex. No. 119b Second Stage Resin to EtO Molal Ratio 1:5-.. 10 12 0 10 12 10. 4. 52 5.42 4.81 5.48 6.58 5.94 140 160 1%: S Ex. No. 1205"--- Third Stage Resin to EtO Molal Ratio 1:10- 5.48 6. 58 5.94 5.48 6. 58 10.85 160 14 8 Ex. No. 1215.....

Fourth Stage i i i i ii 9 9 9 o a atio 1:15. 4. 1 4. 0. 4. 1 4. 13. 180 1 Ex. N0. 122b 17 1% vs Fifth Stage ii i i i? a s 72 68 a o a atio 1:20 .10 0. .10 3.72 13.43 320 Ex. No. 123b 170 54 vs Phenol for resin: Para-octylphenol Aldehyde for resin: Formaldehyde Date, June 23, 24, 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to So of Patent 2,499,370 but this batch designated 11411.]

- Mix Which is Mix Which Re- Starting Mix at fi of Removed for mains as Next em 1011 Sample Starter Max. Max. Time Pressure Temp era- Solubility 1 .10 3. r bs. l lbls. I bs. Lbs Ibls. r bs. Lbs lbls. Ifibs. Lbs

o eso eso eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to Eton Mola'l Ratio 121-- 14 2 15.8 0 14.2 15.8 3.25 3.1 3.4 0.75 11.1 12.4 2.5 50 150 1%: NS Ex. No. 1145-.."

Second Stage Resin to EtO Molal Ratio 1:5 11 1 12.4 2.5 11.1 12.4 12.5 7.0 7. 82 7.88 4.1 4.58 4.62 171 36 SS Ex. No. b.

Third Stage Resin to EtO Molal Ratio 1:10- 6 64 7.36 0 6.64 7.36 15.0 190 1% 8 Ex. No. 116b----- Fourth Stage Resin to EtO Molnl Ratio 1:15- 4.40 4.9 0 4.4 4.9 14.8 400 36 VS Ex. N0. 117b-.

Fifth Stage I Resin to EtO-... Molal Ratio 1:20- 4.1 4.58 4.62 4.1 4.58 18.52 260 172 3% VS Ex. No. 118i).--

S =Solub1e. NS==Notso1nble. SS=Somewhat soluble. VS=Very soluble.

Phenol for resin: Menthylphenol Aldehyde for resin: Formaldehyde Date, July 8-13, 1948 [Resin made in pilot plant size hatch, approximately 25 pounds, corresponding to 69a of Patent 2,499,370 but this batch designated 11%.]

S Soluble. N S-Not soluble. VS Very soluble.

Phenol for resin: Para-secondary butylphenol Date, iul 14-15, 1948 Aldehyde for resin: Formaldehyde [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 2a of Patent 2,499,370 but this batch designated 1240.]

. Alix Which is Mix W'hich Restarting Mix 3 22 of Removed for mains as Next Sample Starter Max. Max. Time Pressu re Temp emhrs. Solubility Is/os. gas. Lbs I b s. Ifibs. Lbs I b s. Ifibs. Lbs lslbls. Ifibs. Lbs

oles- 0- es- .o-- es- 0- es-v vent in Eto vent in a vent in hto vent in Etov First Stays Resin to E tO v V M0121 Ratio 1:1 14.45 15.55 0 14.45 15.55 -4. 25 5.97 6.38 1. 75 8. 48 i 9.17 2.50 60 150 V 7in N3 Ex. No. 1241;

Second Sluge Resin to EtO Molal Ratio 1:51.. 8.48 9.17 2.50 8. 48 9.17 16.0 5.83 6.32 11.05 2.65 2.85 4.95 95 188 3 SS Ex. No. 1251:

Third Stage Resin to E tO Molal Ratio 1:10. 4.82 5.18 0 4.82 5.18 14. l- 400 183 S Ex. No. 126b Fourth Stage Resin to Eton..- Molal Ratio 1:15- 3.85 4.15 0 3.85 4.15 17.0 120 180 3% VS Ex. No. 127!) Fifth Stage Resin to EtO M0121 Ratio 1:20- 2.65 2.85 4. 95 2.65 2.85 15.45 80 170 M2 VS Ex. No. 128b S=Soluble. NS =Not soluble.

Date August 12-13,

Phenol for resin. Menthyl 1 VS=Very soluble.

Aldehyde for resin: Propionaldehyde [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 81a of Patent 2,499,370 but this batch designated 129m] Mix W hieh is Mix Which Re- Starting Mix M figg figg of Removed for mains as Next Sample Starter Max. Max. Time Pressurev Temp erahrs Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs. Sol Res- Eto Sol- Res- Eto Sol- Res Eto Sol- Res- Eto vent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 1' 12.8 17.2 12.8 17.2 2.75v 4.25 5.7 0.95. 8.55 11. 1.80 110 150 $2; Not soluble. Ex. No. 1291) Second Stage Resin to EtO Molal Ratio 8.55 11.50 1. 8155. 11.50 9. 3 4. 78 6.42 5. 2 3. 77 5.08 4.10 170 l Somewhat Ex. N0. b soluble.

Third Stage Resin to EtO Molal Ratio 3.77 5.08 4.10 3.77 5.08 13.1 100 182 M: Soluble. Ex. No. 131b Fourth Stage Resin to Et0- I 7 Molal Ratio 1: 5.2 7.0 5.2 7.0 17.0 3.10 4.17 10.13 2.10 2.83 6.87 200 182 V; Very soluble. Ex. No. 13211.. a

Fifth Stage Resin to EtO- Molal Ratio 1:20- 2. 10 2. 83 6.87 2.10 2. 83 9.12 90 verysoluble. Ex.N0.l33b

Phenol for resin: Para-tertiary amylphenol Aldehyde for resin: Furfural Date, August 27-31, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2,499,370 but this batch designated as 134a.1

- Mix Which is Mix Which Re- Starting Mix Mlfiat End of Removed for mains as Next eaction Sample Starter Max. Max. Time Pressure Temp erahrs. Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Sol- Res- E1 801- Res- 528 801- Res- 5 ;5- SOl- Resvent in vent in vent in vent in 18. 0 11. 2 18. 0 3. 5 2. 75 4. 4 .0. 85 8. 13. 6 2. 65 120 135 }6 Not soluble.

Second Stage Resin to EtO Molal Ratio 1 8.45 13.6 2. 65 8.45 13.6 12.65 3.03 8.12 7.55 3.42 5.48 5.10 110 150 $4 Somewhat Ex. No. 13512. soluble.

Third Stage Resin to EtO M0121 Ratio 1:10-- 4 5 8.0 4.5 8.0 14.5 2.45 4.35 7.99 2.05 3. 65 6. 180 163 14 501111316. Ex. No. 13Gb Fourth Stage Resin to EtO M0181 Ratio 1:15 3.42 5.48 5.10 3. 42 5.48 15.10 180 188 is Very soluble.

Ex. No. 1375 Fifth Stage Resin to EtO 1 Molal Ratio 1:20 2.05 3. 6.60 2. 05 3. 65 13.35 120 125 14 Very soluble. Ex. N0. 138!) Phenol for resin: M enthyl Aldehyde for resin: Furfural Date, Sept. 23-24, 1948 [Resin made on pilot size batch, approximately 25 pounds, corresponding to 89a of Patent 2,409,370 but this batch designated as 139a.]

Mix Which is Mix Which Re- Starting Mix ggg ggg of Removed for mains as Next a Sample Starter Max. Max. Time I Pressure Temp erahrs. Solubility Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Sol- Res- Sol- Res- Sol- Res- Sol- Res- 1 1 vent in vent in vent in vent in FirstStage f Resin t0 EtO Molal Ratio 1:1--- 10 25 17.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 156 }6 Not Soluble. Ex. No. 13% Second Stage Resin to E110-.-" M0131 Ratio1:5 7 6 13. 15 1. 85 7.6 13. 15 9.35 5.2 9.00 6.40 2.4 4.15 2. 80 177 16 Somewhat Ex. N o. 1405.--"- soluble. 0 Third btage Resin to EtO 3 Molal Ratio 1:10-- 4.22 6.98 4. 22 6.98 10.0 90 165 A Soluble. Ex. N 0. 141b Fourth Stage Resin to EtO Molal Ratio 1:15-- 3.76 6.24 3.76 6.24 13.25 171 V3 Verysoluble Ex. No. 14211 Fifth Stage Resin to Et0 Mola] Ratio 1:20..- 2 4 4.15 2.95 2.4 4.15 11.70 90 96 Verysoluble. Ex. No. 1435 Date, October 7-8, 1948 [Resin made on pilot plant si Phenol for resin: Para-octyl Aldehyde for resin: Furfural 2e batch, approximately25 pounds, corresponding to 42a of Patent 2,499,370 with 206 parts by weight of commercial Date, October 11-13, 1948 pala-octylphenol replacing 164 parts by weight of, para-tertiary amylphenol but this batch designated as 14441.]

* Mix Whieh-is I Mix which Re- Starting Mix figsg g of Removed formains as Next Sample Starter Max. Max. Time Pressure Ternge'rahm Solubility gbls. Ifibs. Lsbls. gb's. M 156 kbs. LBS 1 6 'lfi'bs. Lbs

o es- 0 es- 1 o eso 4 es-- vent in Eto vent in vent in Eto vent in First Stage Resin to EtO v I Molal Ratio 1:1.-. 12.1 18.6 12.1 18.6 3.0 5. 38 '8. 28 1. 34 6.72 10. 32 1. 66 80 150 M: Insoluble. Ex. No. 1441;-.."

Second Stage Slight tend- Resin to EtO. ency to M01211 Ratio 115-. 9. 14. 25 9. 25 14. 25 11.0 3. 73 5. 73 4.44 5.52 8. 52 6. 56' 100 177 i2 ward be- Ex. Nb. 145b coming soluble.

Third Stage Resin to Et0. M0121 Ratio 1:10. 6. 72 10.32 1. 66 6. 72 10. 32 14. 91 4. 97 7. 62 11. 01 1. 2. 70 '3. 90 182 $4 Fairly solu- Ex. No. 1460""- ble.

Fourth Stage Resin to 13110.... -Molal Ratio 1:15 5. 52 8.52 6. 56 5. 52 8. 52 19. 81 100 176 54 Readily sol- Ex. No. 147buble.

Fifth Stage Resin to EtO Molal Ratio 1:20. 1. 75 2. 70 3. 1. 75 2. 70 8.4 80' $4 Quite solu- Ex. No. 148b..-. ble.

Phenol for' res'in: Para-phenyl Aldehyde ferns-in: Furfural [Resin made 'on pilot'plant sizebatch, approximately 25 pounds, corresponding to'42a of Patent 2,499,370 with 170 parts by weight of commercial paraphenylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 149m] Mix Which is Mix Which Rm Starting Mix figg figg of Removed for mains as Next Sample Starter Max Max Time Pressure Temp erahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.. Lbs. Sol- Res- Sol- Res- S01- Res- Sol- Restrout in vent in vent in vent in.

First Stage -Resin to Et0...

Molal Ratio 121-- 13.9 16.7 13.9 16.7 3.0 3.50 4.25 0.80 10.35 12.45 2. 20 100 Insoluble. Ex. No.149b- Second Stage Resin to Et0. Slight M0181 Ratio 1=5 10.35 12. 45 2.20 10.35 12. 45 12.20 5.15 6.19 6.06 5. 20 6.26 6.14 so 183 16 Ex. N0. 150b-. 9

Third Stage Resin to EtO. Molal Ratio 1:10. 8.90 10.7 8.90 10.70 19.0 5.30 6.38 11.32 3.60 4.32 7.68 90 193 712 Fairly S0111. Ex. No. 1510..... ble.

Fourth Stage Resin to mom- Molal Ratio 1:15 5.20 6.26 6.14 5.20 6. 26 16.64 100 171 1'6 Readily sol- Ex. No. 152b. uble.

Fifth Stage Resinto 13tO Molal Ratio 1:20. '3. 60 4.32 7.68 3.60 4.32 15.68 Sample somewhat rubbery and gelab 230 2 Ex. No.153b-.. 1 V -inousbu't-fairly soluble 1 1 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A PHYDROPHILE QUATERNARY AMMONIUM COMPOUND OBTAINED BY REACTION BETWEEN A BASIC ACYLATED AMINO-ALCOHOL, IN WHICH THERE IS AT LEAST ONE OCCURRENCE OF THE RADICAL 